6380 J . Org. Chem., Vol. 65, No. 20, 2000
Basel and Hassner
1,3-Di-(ter t-b u t oxyca r b on yl)b en zim id a zolid in -2-on e
1H), 3.75 (s, 3H), 3.31 (m, 1H), 3.21 (m, 1H), 1.49 (s, 9H), 1.44
(s, 9H); 13C NMR δ 170.95, 168.34, 154.97, 85.43, 79.98, 52.53,
52.25, 33.08, 28.22, 28.06; MS m/z (CI/NH3) 353 (MNH4+, 23),
336 (MH+, 100), 297 (22), 280 (24), 236 (35); HRMS calcd for
C14H26NO6S 336.1480, found 336.1515.
1
(15d ): white solid; mp 142-144 °C; H NMR δ 7.88 (m, 2H),
7.23 (m, 2H), 1.67 (s, 18H); 13C NMR δ 148.32, 147.19, 125.99,
124.19, 113.87, 85.16, 27.91; MS m/z (CI/NH3) 335 (MH+, 6),
235 (8), 136 (100); HRMS calcd for C17H22N2O5 344.1528, found
344.1516.
N,O-Di-(ter t-bu toxyca r bon yl)-N-ben zyleth a n ola m in e
(47a ): colorless oil; 1H NMR δ (two rotomers) (a) 7.35-7.14
(m, 5H), 4.50 (s br, 2H), 4.12 (s br, 2H), 3.38 (s br, 2H), 1.52-
1.42 (m, 18H); (b) 7.35-7.14 (m, 5H), 4.50 (s br, 2H), 4.16 (s
br, 2H), 3.48 (s br, 2H), 1.52-1.42 (m, 18H); 13C NMR δ (two
rotomers) 155.28, 153.05, 138.05, 138.82, 128.24, 127.50,
126.92, 81.66, 79.74, 64.47, 64.29, 51.37, 50.37, 45.20, 44.89,
28.08, 27.47; MS m/z (dci/CH4) 352 (MH+, 10), 296 (10), 240
(100); HRMS calcd for C19H30NO5 352.2123, found 352.2080.
O-(ter t-Bu toxyca r bon yl)-N-ben zyleth a n ola m in e (48a ):
ter t-Bu tyl cyclop en tyl d ica r bon a te (22f): colorless oil;
1H NMR δ 5.25-5.15 (m, 1H), 1.92-1.83 (m, 4H), 1.82-1.71
(m, 2H), 1.69-1.58 (m, 2H), 1.53 (s, 9H); 13C NMR δ 148.61,
146.41, 85,58, 83.23, 32.46, 27.41, 23.48; MS m/z (dci/CH4) 231
(MH+, 13), 131 (100); HRMS calcd for C11H19O5 231.1232, found
231.1190.
1
ter t-Am yl ter t-bu tyl d ica r bon a te (22i): colorless oil; H
NMR δ 1.82 (q, J ) 7.5 Hz, 2H), 1.52 (s, 9H), 1.49 (s, 6H),
0.93 (t, J ) 7.5 Hz, 3H); 13C NMR δ 146.76, 146.63, 87.72,
+
1
85.11, 32.95, 27.35, 24.76, 8.02; MS m/z (CI/NH3) 250 (MNH4
,
colorless oil; H NMR δ 7.35-7.21 (m, 5H), 4.19 (t, J ) 5.75
100); HRMS calcd for C11H21O5 233.1389, found 233.1336.
Hz, 2H), 3.82 (s, 2H), 2.90 (t, J ) 5.75 Hz, 2H), 1.48 (s, 9H);
13C 153.04, 139.42, 127.99, 127.74, 126.62, 81.74, 66.03, 53.16,
47.06, 27.32; MS m/z (dci/CH4) 252 (MH+, 100), 196 (93), 152
(17); HRMS calcd for C14H22NO3 252.1594, found 252.1577.
Di(N-(ter t-bu toxyca r bon yl)-N-ben zyla m in oeth yl) ca r -
bon a te (49a ): colorless oil; 1H NMR δ (two rotomers) (a) 7.38-
7.16 (m, 10H), 4.51 (s br, 4H), 4.23 (s br, 4H), 3.49 (s br, 4H),
1.50 (s, 18H); (b) 7.38-7.16 (m, 10H), 4.49 (s br, 4H), 4.16 (s
br, 4H), 3.40 (s br, 4H), 1.44 (s, 18H); 13C NMR δ (two rotomers)
155.57, 154.84, 138.16, 137.90, 128.53, 127.75, 127.27, 80.23,
66.06, 65.80, 51.68, 50.67, 45.35, 44.97, 28.33; MS m/z (dci/
CH4) 529 (MH+, 1), 429 (55), 373 (100), 178 (90); HRMS calcd
for C29H41N2O7 529.2913, found 529.2915;
O ,O ′-D i(t er t -b u t o x y c a r b o n y l)-1,2-t r a n s-c y c lo h e x -
1
a n ed iol (26d ): white solid; mp 67-69 °C; H NMR δ 4.66-
4.54 (m, 2H), 2.18-2.07 (m, 2H), 1.80-1.66 (m, 2H), 1.48 (s,
18H), 1.47-1.37 (m, 4H); 13C NMR δ 152.84, 81.92, 76.41,
29.91, 27.74, 23.25; MS m/z (dci/CH4) 317 (MH+, 2), 261 (27),
205 (61), 98 (100); HRMS calcd for C16H29O6 317.1964, found
317.1940.
Di(2-tr a n s-O-(ter t-b u t oxyca r b on yl))cycloh exyl) ca r -
1
bon a te (27d ): white solid; mp 116-118 °C; H NMR δ 4.62
(m, 4H), 2.15 (m, 4H), 1.71 (m, 4H), 1.48 (s, 9H), 1.47 (s, 9H),
1.48-1.26 (m, 8H); 13C NMR δ 153 90, 153.45, 82.10, 77.29,
77.26, 76.14, 75.57, 29.84, 29.77, 29.63, 29.50, 27.77, 23.16,
23.13, 22.94, 22.91; MS m/z (dci/CH4) 459 (MH+, 1), 347 (23),
303 (15), 205 (33), 143 (61), 98 (100); HRMS calcd for C23H39O9
459.2594, found 459.2606.
ter t-Bu tyl ca r bon ic N-ben zyl-(N-h yd r oxyleth yl) ca r -
ba m ic a n h yd r id e (51a ): colorless oil; 1H NMR δ (two
rotomers) (a) 7.40-7.22 (m, 5H), 4.63 (s, 2H), 3.71 (t, J ) 5.75
Hz, 2H), 3.36 (t, J ) 5.75 Hz, 2H), 1.54 (s, 9H); (b) 7.40-7.22
(m, 5H), 4.58 (s, 2H), 3.78 (t, J ) 5.75 Hz, 2H), 3.44 (t, J )
5.75 Hz, 2H), 1.51 (s, 9H); 13C NMR δ (two rotomers) 150.94,
150.76, 147.71, 147.45, 136.34, 136.13, 128.74, 128.00, 127.78,
85.05, 60.50, 60.43, 52.56, 51.57, 49.79, 49.12, 27.35; MS m/z
(CI/NH3) 313 (MNH4+, 12), 296 (MH+, 5), 252 (78), 196 (62),
152 (100); HRMS calcd for C15H22NO5 296.1497, found 296.1507.
ter t-Bu tyl ca r bon ic N-ben zyl-N-(2-(ter t-bu toxyca r bo-
n yloxy)eth yl) ca r ba m ic a n h yd r id e (52a ): colorless oil; 1H
NMR δ (two rotomers) (a) 7.39-7.23 (m, 5H), 4.60 (s, 2H), 4.14
(t, J ) 5.75 Hz, 2H), 3.45 (t, J ) 5.75 Hz, 2H), 1.51 (s, 9H),
1.48 (s, 9H); (b) 7.39-7.23 (m, 5H), 4.57 (s, 2H), 4.23 (t, J )
5.75 Hz, 2H), 3.53 (t, J ) 5.75 Hz, 2H), 1.55 (s, 9H), 1.49 (s,
9H); 13C NMR δ (two rotomers) 153.00, 150.48, 150.10, 147.20,
147.16, 135.94, 128.79, 128.76, 128.07, 127.88, 127.85, 127.40,
84.94, 84.87, 82.37, 82,24, 63.96, 52.22, 51.30, 45.89, 45.36,
27.56, 27.32, 27.27; MS m/z (CI/NH3) 413 (MNH4+, 100), 352
(22), 313 (56), 252 (75); HRMS calcd for C20H29N2O7 395.2022,
found 396.2050.
ter t-Bu tyl ca r bon ic N-m eth yl-N-(2-(ter t-bu toxyca r bo-
n yloxy)eth yl) ca r ba m ic a n h yd r id e (52b): colorless oil; 1H
NMR δ (two rotomers) (a) 4.25 (t, J ) 5.5 Hz, 2H), 3.58 (t, J
) 5.5 Hz, 2H), 3.03 (s, 3H), 1.54 (s, 9H), 1.49 (s, 9H); (b) 4.19
(t, J ) 5.5 Hz, 2H), 3.54 (t, J ) 5.5 Hz, 2H), 3.04 (s, 3H), 1.53
(s, 9H), 1.49 s, 9H); 13C NMR δ (two rotomers) 153.18, 150.19,
149.95, 147.41, 84.92, 82.60, 82.46, 64.22, 64.13, 48.61, 48.45,
36.41, 35.88, 27.69, 27.45; MS m/z (CI/NH3) 320 (MH+, 5), 237
(77), 220 (31), 176 (32), 137 (38), 120 (100); HRMS calcd for
O-(ter t-Butoxycar bon yl)-1,2-tr a n s-cycloh exan ediol(28d):
colorless oil; 1H NMR δ 4.36 (dtt, J ) 15, 10, 4.5 Hz, 1H), 3.58
(dtt, J ) 15, 10, 4.5 Hz, 1H), 2.17-2.08 (m, 2H), 1.78-1.65
(m, 2H), 1.50 (s, 9H), 1.39-1.21 (m, 4H); 13C NMR δ 153.49,
82.32, 81.11, 72.65, 32.84, 29.95, 27.76, 23.93, 23.79; MS m/z
(dci/CH4) 217 (MH+, 97), 161 (100); HRMS calcd for C11H21O4
217.1439, found 217.1431.
2-tr a n s-(O-(ter t-Bu toxyca r bon yl))cycloh exyl
2′-(1′-
m eth yl)im id a zole ca r boxyla te (29): yellowish oil; 1H NMR
δ 7.14 (d, J ) 1 Hz, 1H), 7.01 (d, J ) 1 Hz, 1H), 5.08 (ddd, J
) 15, 10, 4.5 Hz, 1H), 4.82 (ddd, J ) 15, 10, 4.5 Hz, 1H), 3.99
(s, 3H), 2.17 (m, 2H), 1.77 (m, 2H), 1.70-1.40 (m, 4H), 1.39 (s,
9H); 13C NMR δ 158.32, 152.80, 136.62, 129.41, 126 11, 82.10,
76.11, 74.65, 35.99, 30.01, 29.94, 27.66, 23.32, 23.22; MS m/z
(dci/CH4) 325 (MH+, 100), 269 (15), 220 (27), 205 (37); HRMS
calcd for C16H25N2O5 325.1763, found 325.1779.
O,O′-Di(ter t-bu toxycar bon yl)-1,3-pr opan ediol (32b): col-
1
orless oil; H NMR δ 4.16 (t, J ) 6.5 Hz, 4H), 2.02 (pent, J )
6.5 Hz, 2H), 1.49 (s, 18H); 13C NMR δ 153.41, 82.11, 63.44,
28.11, 27.75; MS m/z (CI/NH3) 297 (MNH4+, 100), 238 (80),
182 (50); HRMS calcd for C13H25O6 277.1651, found 277.1653.
Di(3-(ter t-bu toxyca r bon yloxy)p r op yl) ca r bon a te (33b):
1
colorless oil; H NMR δ 4.24 (t, J ) 7.5 Hz, 4H), 4.16 (t, J )
7.5 Hz, 4H), 2.04 (pent, J ) 7.5 Hz, 4H), 1.49 (s, 18H); 13C
NMR δ 154.92, 153.34, 82.16, 64.43, 63.19, 28.05, 27.72; MS
m/z (CI/NH3) 396 (MNH4+, 74), 340 (18), 284 (100); HRMS
calcd for C17H31O9 379.1968, found 379.1976.
3-(ter t-Bu toxycar bon yl)-5-m eth yloxazolidin -2-on e (37c):
white solid; mp 102-104 °C; 1H NMR δ 4.64 (ddq, J ) 8, 7.25,
6 Hz, 1H), 4.05 (dd, J ) 10, 8 Hz, 1H), 3.50 (dd, J ) 10, 7.25
Hz, 1H), 1.54 (s, 9H), 1.46 (d, J ) 6 Hz, 3H); 13C NMR δ 151.87,
149.53, 83.70, 69.70, 50.06, 27.92, 20.34; MS m/z (dci/CH4) 202
(MH+, 1), 146 (100), 102 (11); HRMS calcd for C9H16NO4
202.1079, found 202.1030.
C
14H26NO7 320.1709, found 320.1726.
Ack n ow led gm en t. Support of this research by a
grant from the Israel Science Foundation and the
Marcus Center for Pharmaceutical and Medicinal Chem-
istry is gratefully acknowledged.
3-(ter t-Bu toxyca r bon yl)-4-(m eth oxyca r bon yl)th ia zoli-
1
d in -2-on e (42): yellow oil; H NMR δ 4.99 (dd, J ) 8.5, 2.25
Su p p or tin g In for m a tion Ava ila ble: Copies of 1H and 13C
NMR spectra of new compounds and a copy of 19F NMR
spectrum for 2c. Characterization data for compounds 2h ,
5b,c, 8b,d , 9d , 10b,f, 12b-d , 16a ,b, 26b,c, 27b, 28c, 36d ,
37a ,d , 43, 45, 49b, and 53a ,b. This material is available free
Hz, 1H), 3.84 (s, 3H), 3.64 (dd, J ) 11.75, 8.5 Hz, 1H), 3.32
(dd, J ) 11.75, 2.25 Hz, 1H), 1.51 (s, 9H); 13C NMR δ 169.74,
168.79, 148.48, 84.42, 59.37, 53.40, 27.75, 27.35; MS m/z (CI/
NH3) 279 (MNH4+, 7), 179 (100), 162 (42); HRMS calcd for
C
10H15NO5S 261.0670, found 261.0667.
N,S-Di(ter t-bu toxyca r bon yl)cystein e m eth yl ester (44):
white solid; mp 52-54 °C; 1H NMR δ 5.37 (s br, 1H), 4.55 (m,
J O000257F